CN104198554A - Working electrode and preparation method thereof as well as biosensor - Google Patents
Working electrode and preparation method thereof as well as biosensor Download PDFInfo
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- CN104198554A CN104198554A CN201410445152.2A CN201410445152A CN104198554A CN 104198554 A CN104198554 A CN 104198554A CN 201410445152 A CN201410445152 A CN 201410445152A CN 104198554 A CN104198554 A CN 104198554A
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Abstract
The invention relates to the technical field of electrochemistry and in particular relates to a working electrode and a preparation method thereof as well as a biosensor. The raw material of the working electrode is active carbon, wherein the preparation method of the working electrode comprises the following steps: forming, oxidizing, modifying nano-metal, carrying out silanization, grafting glutaraldehyde and immobilizing biological enzyme; the diameter of the working electrode is 0.5-10mm; the length of the working electrode is 1-10cm; the iodine sorption value is 700-2500mg/g; the specific surface area is 700-3500m<2>/g; the ash content is less than or equal to 4%. The immobilization amount of the biological enzyme in the working electrode is obviously improved and can reach 52.5mg/g; meanwhile, the working electrode is high in sensitivity and high in capacity of resisting disturbance. The working electrode in the biosensor is dismountable and is easy to replace; the biosensor is easy to operate and capable of continuously measuring; to-be-detected liquid is placed independently, so that samples are simple and convenient to feed and discharge; due to the arrangement of a magnetic stirring rotor, the detection sensitivity can be further improved.
Description
Technical field
The present invention relates to technical field of electrochemistry, particularly a kind of working electrode and preparation method thereof, biology sensor.
Background technology
Due to the change of growth in the living standard, dietary structure, rhythm of life and the few moving factors such as life style of sitting that day is becoming tight more, whole world onset diabetes rate rapid development, diabetes have become the chronic disease of the third-largest serious threat human health after tumour, cardiovascular pathological changes.Current global diabetic has surpassed 1.2 hundred million people, the Chinese patients people the second in the world of live in groups, and the onset diabetes rate of China is up to 9.6%, and in future 50 years, diabetes will be Chinese serious public health problems.
Diabetes can cause serious complication, as diabetic ketoacidotic coma, diabetes Hyperosmotic coma, diabetic eye diseases, diabetic nephropathy etc., have a strong impact on diabetic's quality of life.Current studies have shown that, strictly controls blood sugar and can make the danger of diabetic's death decline, the generation of minimizing or delaying complications of diabetes.Visible, the key for the treatment of diabetes is strictly to control blood sugar.The strict blood sugar of controlling needs diabetic that glycemic control is arrived normal or approaches normal level, and fasting blood glucose level is 6.1mmol/L, and 2 hours blood glucose levels are 7.8mmol/L after the meal.Therefore the concentration that, fast, accurately detects glucose in blood is significant for monitoring diabetes.
At present, glucose biological sensor becomes the important tool of glucose detection, and selectivity and sensitivity that it is good arouse great concern.The principle that glucose biological sensor detects glucose is: glucose biological sensor is by the glucose generation redox reaction in the glucose oxidase on electrode and reaction tank solution, glucose is oxidized, glucose oxidase is reduced, by electronics, transmit medium the glucose oxidase of reduction-state is recovered to ortho states, continue to occur redox reaction.Glucose biological sensor is to utilize electrochemical reaction, forms electron stream, and sense terminals is collected this current and voltage signals, utilizes the linear relationship of curtage signal and concentration of glucose, realizes the detection of glucose in solutions concentration.
Yet, working electrode in glucose biological sensor is glass-carbon electrode, it can not directly carry out physical method or chemical method enzyme immobilization, can only process by carry out other on glass-carbon electrode surface, and for example chemical crosslinking or collosol and gel make the immobilized a small amount of enzyme in glass-carbon electrode surface.Because the enzyme immobilization amount of glass-carbon electrode is low, make its sensitivity fail to reach desirable level.Therefore, provide a kind of enzyme supported quantity working electrode high, that sensitivity for analysis is high to have important practical significance.
Summary of the invention
In view of this, the invention provides a kind of working electrode and preparation method thereof, biology sensor.This working electrode has obtained significant raising to the supported quantity of biology enzyme, and biology enzyme supported quantity can reach 52.5mg/g, and this working electrode highly sensitive, antijamming capability is strong; Working electrode in biology sensor provided by the invention is detachable, changes simply, and working electrode can reuse, and has extended the serviceable life of biology sensor; Biology sensor easy operating, can continuous coverage; And liquid to be measured independently exists, turnover sample is easy; The setting of magnetic agitation rotor can further improve detection sensitivity.
In order to realize foregoing invention object, the invention provides following technical scheme:
The invention provides a kind of working electrode, its raw material is activated charcoal, through moulding, oxidation, decorated nanometer metal, silanization, grafting glutaraldehyde, immobilized biology enzyme, obtains;
The diameter of working electrode is 0.5～10mm, and length is 1～10cm, and iodine sorption value is 700～2500mg/g, and specific surface area is 700～3500m
2/ g, ash content≤4%.
The present invention, by active carbon forming, decorated nanometer metal, immobilized biology enzyme, makes working electrode, and this working electrode is due to self pore passage structure and the absorption affinity modification of being convenient to nano material and enzyme immobilized.Test findings shows that the nano-metal particle of modifying is orderly and particle is smooth evenly, be conducive to improve electric conductivity and the sensitivity of electrode, and the space between nano particle is also conducive to the raising of enzyme supported quantity, by the immobilized enzyme difficult drop-off that makes of covalency, can improve enzyme performance, make enzymatic reaction more abundant, extended the serviceable life of enzyme simultaneously.
The present invention has obtained significant raising to the supported quantity of biology enzyme, and biology enzyme supported quantity can reach 52.5mg/g; And this working electrode highly sensitive, antijamming capability is strong.
As preferably, iodine sorption value is 700～850mg/g.
As preferably, specific surface area is 950～1100m
2/ g.
In embodiment more provided by the invention, working electrode is cylindrical.But the shape of working electrode is not limited to this in the present invention, those skilled in the art think that feasible shape is all within protection scope of the present invention, and the present invention does not limit at this.
In embodiment more provided by the invention, activated charcoal is coal mass active carbon or cocoanut active charcoal.
In embodiment more provided by the invention, nano metal is nm of gold, Nano Silver, Nanometer Copper or Platinum Nanoparticles.
In embodiment more provided by the invention, biology enzyme is glucose oxidase, hydrogen peroxidase, papain, AMS or urase.
The present invention also provides the preparation method of this working electrode, comprises the steps:
Steps A: get activated charcoal, through moulding, obtain pressed active carbon;
Step B: get pressed active carbon, through oxidation, decorated nanometer metal, silanization, grafting glutaraldehyde, immobilized biology enzyme, obtain.
As preferably, the diameter 0.5～10mm of working electrode, length 1～10cm, iodine sorption value 700～2500mg/g, specific surface area 700～3500m
2/ g, ash content≤4%.
Preferably, iodine sorption value is 700～850mg/g.
Preferably, specific surface area is 950～1100m
2/ g.
In embodiment more provided by the invention, decorated nanometer metal implement body is:
The activated charcoal of take after oxidation is working electrode, arranges electrode and contrast electrode, adopts cyclic voltammetry electro-deposition nanometer cobalt; Activated charcoal after depositing nano cobalt is immersed in nano metal solution and modified;
Repeat aforesaid operations 1～20 time.
As preferably, the reagent that electro-deposition nanometer cobalt adopts is 0.01～1mol/L Na
2sO
4mixed solution with 5～50mmol/L cobalt acetate.
Preferably, the reagent that electro-deposition nanometer cobalt adopts is 0.01～0.1mol/L Na
2sO
4mixed solution with 5～10mmol/L cobalt acetate.
As preferably, the parameter of cyclic voltammetry is set to: sweeping speed is 1～100mv/s, sweep limit :-0.9～0.5V, the scanning number of turns: 1～400.
Preferably, the parameter of cyclic voltammetry is set to: sweeping speed is 10～50mv/s, sweep limit :-0.9～0.5V, the scanning number of turns: 20～100.
In embodiment more provided by the invention, nano metal solution is tetra chlorauric acid solution, silver nitrate, cupric chloride, chloroplatinic acid or thiocyanation iron.
As preferably, the concentration of nano metal solution is 0.1～50mmol/L.
As preferably, the time of modification is 5～40min.
In embodiment more provided by the invention, activated charcoal is coal mass active carbon or cocoanut active charcoal.
In embodiment more provided by the invention, nano metal is nm of gold, Nano Silver, Nanometer Copper or Platinum Nanoparticles.
In embodiment more provided by the invention, biology enzyme is glucose oxidase, hydrogen peroxidase, papain, AMS or urase.
The present invention also provides the application of this working electrode in preparing biology sensor.
The present invention also provides a kind of biology sensor, this biology sensor comprises working electrode 1 provided by the invention, to electrode 2, contrast electrode 3, magnetic agitation rotor 4, shell 5, signal processor 6, aquarium 7, liquid outlet switch 8, liquid outlet 9, liquid inlet 10, electrode fixed body 11, reaction tank 12, screw 13, concrete annexation is:
Working electrode 1, electrode 2 and contrast electrode 3 are fixed in electrode fixed body 11, working electrode 1 is fixed on electrode fixed body 11 by screw 13; Magnetic agitation rotor 4 is fixed on aquarium 7, and electrode fixed body 11 forms reaction tank 12 with aquarium 7;
Aquarium 7 has liquid inlet 10 and liquid outlet 9, and liquid outlet 9 is provided with liquid outlet switch 8; Liquid inlet 10 is connected with liquid input media to be measured, and liquid outlet 9 is connected with waste liquid bottle;
Electrode fixed body 11 is embedded on shell 5 and by wire and connects signal processor 6.
Biology sensor provided by the invention take that the present invention makes through nano metal modify, the activated carbon electrodes of immobilized biology enzyme is working electrode, the biology enzyme supported quantity of this working electrode can reach 52.5mg/g, highly sensitive, antijamming capability is strong; This working electrode is detachable, changes simply, and working electrode can reuse, and has extended the serviceable life of biology sensor.Biology sensor easy operating, can continuous coverage; And liquid to be measured independently exists, turnover sample is easy; The setting of magnetic agitation rotor can further improve detection sensitivity.
As preferably, electrode 2 is made by conductive material.
In embodiment more provided by the invention, electrode 2 is made by platinum, gold, silver or graphite.
As preferably, contrast electrode 3 is saturated calomel electrode, and internal-filling liquid body is saturated potassium chloride.
As preferably, electrode fixed body 11 is made by polytetrafluoroethylmaterial material.
Sensor provided by the invention should clean aquarium 7 before measuring sample; After liquid to be measured injects, start magnetic agitation rotor 4; Electrode inserts in liquid to be measured by wire and signal processor 6 linkage record electric current and voltages, according to the linear relationship of response current and concentration of glucose, shows the concentration of glucose of liquid to be measured at display window.
The invention provides a kind of working electrode and biology sensor.The raw material of this working electrode is activated charcoal, through moulding, oxidation, decorated nanometer metal, silanization, grafting glutaraldehyde, immobilized biology enzyme, obtains; The diameter of working electrode is 0.5～10mm, and length is 1～10cm, and iodine sorption value is 700～2500mg/g, and specific surface area is 700～3500m
2/ g, ash content≤4%.Working electrode provided by the invention has obtained significant raising to the supported quantity of biology enzyme, and biology enzyme supported quantity can reach 52.5mg/g, and this working electrode highly sensitive, antijamming capability is strong.
Working electrode in biology sensor provided by the invention is detachable, changes simply, and working electrode can reuse, and has extended the serviceable life of biology sensor; Biology sensor easy operating, can continuous coverage; And liquid to be measured independently exists, turnover sample is easy; The setting of magnetic agitation rotor can further improve detection sensitivity.
Accompanying drawing explanation
Fig. 1 shows the SEM schematic diagram of nanometer cobalt in embodiment 1;
Fig. 2 shows the SEM schematic diagram of nm of gold in embodiment 1;
Fig. 3 shows the typical curve of glucose oxidase enzyme concentration and absorbance in embodiment 1;
Fig. 4 shows the curve map of the immobilized glucose oxidase amount of working electrode in embodiment 1;
Fig. 5 shows the concrete annexation of biology sensor in embodiment 4;
Fig. 6 shows the current-responsive of biology sensor under different concentration of glucose in embodiment 4;
Fig. 7 shows the current-responsive of biology sensor to uric acid, ascorbic acid, glucose in embodiment 4.
Embodiment
The invention discloses a kind of working electrode and preparation method thereof, biology sensor, those skilled in the art can use for reference content herein, suitably improve technological parameter and realize.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the artly, they are all deemed to be included in the present invention.Method of the present invention and application are described by preferred embodiment, related personnel obviously can change methods and applications as herein described or suitably change and combination within not departing from content of the present invention, spirit and scope, realizes and apply the technology of the present invention.
Raw materials used in working electrode provided by the invention and preparation method thereof, biology sensor, reagent or material all can be buied by market.
Below in conjunction with embodiment, further set forth the present invention:
The preparation of embodiment 1 working electrode
Activated charcoal (coal mass active carbon) is shaped to cylindric, diameter 3mm, length 2.2cm, iodine sorption value 800mg/g, specific surface area 1000m
2/ g, ash content≤4%.
Take pressed active carbon 4g, with distilled water, boil 30min, filter, repeat aforesaid operations three times, put it in baking oven dry 12h at 110 ℃.
Get dried activated charcoal and be placed in round-bottomed flask, add 100mL, 20%HNO
3solution, oil bath stirring and refluxing reaction 3h at 80 ℃.The filter cake obtaining is after filtration placed in to 500mL beaker, adds 400mL distillation poach 15min, filtration, repetitive operation 3 times.The activated charcoal obtaining is put into drying box, and dry 12h, obtains the activated charcoal after oxidation at 100～120 ℃.
To the Activated Carbon Modification nano metal after the above-mentioned oxidation making, its concrete operations are: the activated charcoal of take after above-mentioned oxidation is working electrode, and Pt is to electrode, and saturated calomel electrode is contrast electrode, at 0.1mol/L Na
2sO
4in the solution of 10mmol/L cobalt acetate, adopt cyclic voltammetry electro-deposition nanometer cobalt, the parameter of cyclic voltammetry is set to: sweep speed for 50mv/s, sweep limit :-0.9～0.5V, the scanning number of turns: 20; By 20min in the tetra chlorauric acid solution of the activated charcoal immersion 25mmol/L handling well.Repeat this operation 3 times, obtain the activated charcoal of decorated nanometer metal.The SEM figure of electro-deposition nanometer cobalt is shown in Fig. 1, and the SEM figure of modified nano gold is shown in Fig. 2.Orderly and the particle of nanogold particle is smooth evenly as seen from Figure 2, the electric conductivity and the sensitivity that are conducive to improve electrode, and also the space between nano particle is also conducive to the raising of enzyme supported quantity, by the immobilized enzyme difficult drop-off that makes of covalency, can improve enzyme performance.
Under nitrogen protection, the toluene by 100mL after molecular sieve drying, the activated charcoal of the above-mentioned decorated nanometer metal making of 1g, 2mL (3-aminopropyl) trimethoxy silane (AMPTS) add in there-necked flask, return stirring 24h at 110 ℃.Heated rear filtration, and rinsed with absolute ethyl alcohol, the surface silicon alkanisation activated charcoal obtaining is placed in apparatus,Soxhlet's and fully extracts 24h, and end product, 80 ℃ of vacuum drying, obtains silanization activated charcoal.
Get the above-mentioned silanization activated charcoal making of 3g in the flask of 150mL, add 100mL ethanol to make solution, the 50wt% glutaraldehyde that adds again 5mL, after 80 ℃ of return stirring 2h, filter, and by distilled water flush cake repeatedly, gained activated charcoal is placed in the dry 24h of 80 ℃ of vacuum dryers, obtains the activated charcoal of grafting glutaraldehyde.
The activated charcoal 0.6g that takes the above-mentioned grafting glutaraldehyde making is placed in the conical flask that 100mL distilled water is housed, and adds 30mg glucose oxidase, and ice bath stirs 24h, obtains working electrode.
The working electrode obtaining is carried out to the detection of biology enzyme supported quantity, and detection method is as follows:
1, the standard curve determination of glucose oxidase enzyme concentration and absorbance
Get totally 6 test tubes 1,2,3,4,5, No. 6, in test tube, add respectively 0,0.2,0.4,0.6,0.8, the glucose oxidase solution of 1.0mL 0.1mg/mL, then, in above-mentioned test tube, add successively 1.0,0.8,0.6,0.4,0.2,0mL distilled water.Finally, in every test tube, all add 5mL Coomassie brilliant blue dye liquor, under room temperature, shake all.No. 1 test tube of take is the absorbance of reference solution in 595nm surveys each pipe.The typical curve of drawing as shown in Figure 3.
2, the detection of biology enzyme supported quantity
Weigh respectively the activated charcoal of the above-mentioned grafting glutaraldehyde making of 1g in conical flask.Add respectively again that concentration is 0.04,0.07,0.1,0.3,0.5mg/mL glucose oxidase solution.Ice bath 24h, filters, and surveys filtrate in the absorbance at 595nm place, according to the typical curve of drawing, calculates biology enzyme supported quantity, and result as shown in Figure 4.
The biology enzyme supported quantity of the working electrode that as seen from Figure 4, embodiment 1 makes reaches 52.5mg/g.
The preparation of embodiment 2 working electrodes
Activated charcoal (cocoanut active charcoal) is shaped to cylindric, diameter 0.5mm, length 1cm, iodine sorption value 700mg/g, specific surface area 1100m
2/ g, ash content≤4%.
Take pressed active carbon 4g, with distilled water, boil 30min, filter, repeat aforesaid operations three times, put it in baking oven dry 18h at 110 ℃.
Get dried activated charcoal and be placed in round-bottomed flask, add 100mL, 20%HNO
3solution, oil bath stirring and refluxing reaction 3h at 80 ℃.The filter cake obtaining is after filtration placed in to 500mL beaker, adds 400mL distillation poach 15min, filtration, repetitive operation 3 times.The activated charcoal obtaining is put into drying box, and dry 18h, obtains the activated charcoal after oxidation at 100～120 ℃.
To the Activated Carbon Modification nano metal after the above-mentioned oxidation making, its concrete operations are: the activated charcoal of take after above-mentioned oxidation is working electrode, and Pt is to electrode, and saturated calomel electrode is contrast electrode, at 0.01mol/L Na
2sO
4in the solution of 5mmol/L cobalt acetate, adopt cyclic voltammetry electro-deposition nanometer cobalt, the parameter of cyclic voltammetry is set to: sweep speed for 10mv/s, sweep limit :-0.9～0.5V, the scanning number of turns: 100; By 40min in the liquor argenti nitratis ophthalmicus of the activated charcoal immersion 0.1mmol/L handling well.Repeat this operation 1 time, obtain the activated charcoal of decorated nanometer metal.
Under nitrogen protection, the toluene by 100mL after molecular sieve drying, the activated charcoal of the above-mentioned decorated nanometer metal making of 1g, 2mL (3-aminopropyl) trimethoxy silane (AMPTS) add in there-necked flask, return stirring 24h at 110 ℃.Heated rear filtration, and rinsed with absolute ethyl alcohol, the surface silicon alkanisation activated charcoal obtaining is placed in apparatus,Soxhlet's and fully extracts 24h, and end product, 80 ℃ of vacuum drying, obtains silanization activated charcoal.
Get the above-mentioned silanization activated charcoal making of 3g in the flask of 150mL, add 100mL ethanol to make solution, the 50wt% glutaraldehyde that adds again 5mL, after 80 ℃ of return stirring 2h, filter, and by distilled water flush cake repeatedly, gained activated charcoal is placed in the dry 24h of 80 ℃ of vacuum dryers, obtains the activated charcoal of grafting glutaraldehyde.
The activated charcoal 0.6g that takes the above-mentioned grafting glutaraldehyde making is placed in the conical flask that 100mL distilled water is housed, and adds 30mg hydrogen peroxidase, and ice bath stirs 24h, obtains working electrode.And it has been carried out to the detection of biology enzyme supported quantity, result shows that the biology enzyme supported quantity of this working electrode reaches 50.8mg/g.
The preparation of embodiment 3 working electrodes
Activated charcoal (coal mass active carbon) is shaped to cylindric, diameter 10mm, length 10cm, iodine sorption value 850mg/g, specific surface area 950m
2/ g, ash content≤4%.
Take pressed active carbon 4g, with distilled water, boil 30min, filter, repeat aforesaid operations three times, put it in baking oven dry 24h at 110 ℃.
Get dried activated charcoal and be placed in round-bottomed flask, add 100mL, 20%HNO
3solution, oil bath stirring and refluxing reaction 3h at 80 ℃.The filter cake obtaining is after filtration placed in to 500mL beaker, adds 400mL distillation poach 15min, filtration, repetitive operation 3 times.The activated charcoal obtaining is put into drying box, and dry 24h, obtains the activated charcoal after oxidation at 100～120 ℃.
To the Activated Carbon Modification nano metal after the above-mentioned oxidation making, its concrete operations are: the activated charcoal of take after above-mentioned oxidation is working electrode, and Pt is to electrode, and saturated calomel electrode is contrast electrode, at 0.09mol/L Na
2sO
4in the solution of 9mmol/L cobalt acetate, adopt cyclic voltammetry electro-deposition nanometer cobalt, the parameter of cyclic voltammetry is set to: sweep speed for 40mv/s, sweep limit :-0.9～0.5V, the scanning number of turns: 30; By 5min in the platinum acid chloride solution of the activated charcoal immersion 50mmol/L handling well.Repeat this operation 20 times, obtain the activated charcoal of decorated nanometer metal.
Under nitrogen protection, the toluene by 100mL after molecular sieve drying, the activated charcoal of the above-mentioned decorated nanometer metal making of 1g, 2mL (3-aminopropyl) trimethoxy silane (AMPTS) add in there-necked flask, return stirring 24h at 110 ℃.Heated rear filtration, and rinsed with absolute ethyl alcohol, the surface silicon alkanisation activated charcoal obtaining is placed in apparatus,Soxhlet's and fully extracts 24h, and end product, 80 ℃ of vacuum drying, obtains silanization activated charcoal.
Get the above-mentioned silanization activated charcoal making of 3g in the flask of 150mL, add 100mL ethanol to make solution, the 50wt% glutaraldehyde that adds again 5mL, after 80 ℃ of return stirring 2h, filter, and by distilled water flush cake repeatedly, gained activated charcoal is placed in the dry 24h of 80 ℃ of vacuum dryers, obtains the activated charcoal of grafting glutaraldehyde.
The activated charcoal 0.6g that takes the above-mentioned grafting glutaraldehyde making is placed in the conical flask that 100mL distilled water is housed, and adds 30mg AMS, and ice bath stirs 24h, obtains working electrode.And it has been carried out to the detection of biology enzyme supported quantity, result shows that the biology enzyme supported quantity of this working electrode reaches 47.3mg/g.
The preparation of embodiment 4 biology sensors
Get working electrode that embodiment 1 makes, to electrode (being made by platinum), contrast electrode (saturated calomel electrode, internal-filling liquid body is saturated potassium chloride), magnetic agitation rotor, shell, signal processor, aquarium, liquid outlet switch, liquid outlet, liquid inlet, electrode fixed body (being made by polytetrafluoroethylmaterial material), reaction tank, screw be assembled into biology sensor, the concrete annexation of this biology sensor is referring to Fig. 5, and concrete annexation is as follows:
Get working electrode (1), electrode (2) and contrast electrode (3) are fixed in electrode fixed body (11), working electrode (1) is fixed on electrode fixed body (11) by screw (13);
Magnetic agitation rotor (4) is fixed on aquarium (7), and electrode fixed body (11) forms reaction tank (12) with aquarium (7);
Aquarium (7) has liquid inlet (10) and liquid outlet (9), and liquid outlet (9) is provided with liquid outlet switch (8); Liquid inlet (10) is connected with liquid input media to be measured, and liquid outlet (9) is connected with waste liquid bottle;
Electrode fixed body (11) is embedded in shell (5) above and connects signal processor (6) by wire.
The above-mentioned biology sensor making is carried out to the detection of current-responsive value and anti-interference, and specifically test and interpretation of result are as follows:
1, the current-responsive under different concentration of glucose
The phosphate buffer that adds 19mL pH=7.0 in aquarium, splashes into 1mL pH=7.0 every 15s, and the glucose solution that concentration is 0.05mol/L records the current-responsive value under its each concentration.Result is as Fig. 6.
As seen from Figure 6, linear relationship is y=0.0026x+0.1445, R
2=0.9976, visible, it is broad that this biology sensor detects the concentration of glucose range of linearity, is 2.5～20.3mmol/L, and current-responsive value reaches microampere order simultaneously, and sensitivity is higher.
2, anti-interference test
The phosphate buffer that adds 20mL pH=7.0 in aquarium, the uric acid, ascorbic acid, the glucose that every 15s, splash into respectively 1mL0.1mol/L obtain corresponding current-responsive.Result is as Fig. 7.
As seen from Figure 7, the working electrode of the present embodiment biology sensor is minimum to the current-responsive of disturbing factor, and glucose is had to extremely strong response, thereby also illustrates that the working electrode that embodiment 1 provides is strong to the selectivity of glucose, strong interference immunity.
The preparation of embodiment 5 biology sensors
Get working electrode that embodiment 2 makes, to electrode (being made of gold), contrast electrode (saturated calomel electrode, internal-filling liquid body is saturated potassium chloride), magnetic agitation rotor, shell, signal processor, aquarium, liquid outlet switch, liquid outlet, liquid inlet, electrode fixed body (being made by polytetrafluoroethylmaterial material), reaction tank, screw be assembled into biology sensor, the concrete annexation of this biology sensor is referring to Fig. 1, and concrete annexation is as follows:
Get working electrode (1), electrode (2) and contrast electrode (3) are fixed in electrode fixed body (11), working electrode (1) is fixed on electrode fixed body (11) by screw (13);
Magnetic agitation rotor (4) is fixed on aquarium (7), and electrode fixed body (11) forms reaction tank (12) with aquarium (7);
Aquarium (7) has liquid inlet (10) and liquid outlet (9), and liquid outlet (9) is provided with liquid outlet switch (8); Liquid inlet (10) is connected with liquid input media to be measured, and liquid outlet (9) is connected with waste liquid bottle;
Electrode fixed body (11) is embedded in shell (5) above and connects signal processor (6) by wire.
The above-mentioned biology sensor making has been carried out to the detection of current-responsive value and anti-interference, current-responsive value and the anti-interference of the biology sensor that result and embodiment 4 make are close, show that the biology sensor that the present embodiment makes detects concentration of glucose range of linearity broadness, sensitivity is higher, and working electrode is strong to the selectivity of corresponding substrate, strong interference immunity.
The preparation of embodiment 6 biology sensors
Get working electrode that embodiment 3 makes, to electrode (being made from silver), contrast electrode (saturated calomel electrode, internal-filling liquid body is saturated potassium chloride), magnetic agitation rotor, shell, signal processor, aquarium, liquid outlet switch, liquid outlet, liquid inlet, electrode fixed body (being made by polytetrafluoroethylmaterial material), reaction tank, screw be assembled into biology sensor, the concrete annexation of this biology sensor is referring to Fig. 1, and concrete annexation is as follows:
Get working electrode (1), electrode (2) and contrast electrode (3) are fixed in electrode fixed body (11), working electrode (1) is fixed on electrode fixed body (11) by screw (13);
Magnetic agitation rotor (4) is fixed on aquarium (7), and electrode fixed body (11) forms reaction tank (12) with aquarium (7);
Aquarium (7) has liquid inlet (10) and liquid outlet (9), and liquid outlet (9) is provided with liquid outlet switch (8); Liquid inlet (10) is connected with liquid input media to be measured, and liquid outlet (9) is connected with waste liquid bottle;
Electrode fixed body (11) is embedded in shell (5) above and connects signal processor (6) by wire.
The above-mentioned biology sensor making has been carried out to the detection of current-responsive value and anti-interference, current-responsive value and the anti-interference of the biology sensor that result and embodiment 4 make are close, show that the biology sensor that the present embodiment makes detects concentration of glucose range of linearity broadness, sensitivity is higher, and working electrode is strong to the selectivity of corresponding substrate, strong interference immunity.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a working electrode, is characterized in that, its raw material is activated charcoal, through moulding, oxidation, decorated nanometer metal, silanization, grafting glutaraldehyde, immobilized biology enzyme, obtains;
The diameter of described working electrode is 0.5～10mm, and length is 1～10cm, and iodine sorption value is 700～2500mg/g, and specific surface area is 700～3500m
2/ g, ash content≤4%.
2. working electrode according to claim 1, is characterized in that, described activated charcoal is coal mass active carbon or cocoanut active charcoal.
3. working electrode according to claim 1, is characterized in that, described nano metal is nm of gold, Nano Silver, Nanometer Copper or Platinum Nanoparticles.
4. working electrode according to claim 1, is characterized in that, described biology enzyme is glucose oxidase, hydrogen peroxidase, papain, AMS or urase.
5. the preparation method of working electrode as described in any one in claim 1 to 4, is characterized in that, comprises the steps:
Steps A: get activated charcoal, through moulding, obtain pressed active carbon;
Step B: get described pressed active carbon, through oxidation, decorated nanometer metal, silanization, grafting glutaraldehyde, immobilized biology enzyme, obtain.
6. preparation method according to claim 5, is characterized in that, described decorated nanometer metal implement body is:
The activated charcoal of take after oxidation is working electrode, arranges electrode and contrast electrode, adopts cyclic voltammetry electro-deposition nanometer cobalt; Activated charcoal after depositing nano cobalt is immersed in nano metal solution and modified;
Repeat aforesaid operations 1～20 time.
7. the application of the working electrode as described in any one in claim 1 to 4 in preparing biology sensor.
8. a biology sensor, it is characterized in that, described biology sensor comprises working electrode (1) as described in any one in claim 1 to 4, to electrode (2), contrast electrode (3), magnetic agitation rotor (4), shell (5), signal processor (6), aquarium (7), liquid outlet switch (8), liquid outlet (9), liquid inlet (10), electrode fixed body (11), reaction tank (12), screw (13), concrete annexation is:
Working electrode (1), electrode (2) and contrast electrode (3) are fixed in electrode fixed body (11), working electrode (1) is fixed on electrode fixed body (11) by screw (13); Magnetic agitation rotor (4) is fixed on aquarium (7), and electrode fixed body (11) forms reaction tank (12) with aquarium (7);
Aquarium (7) has liquid inlet (10) and liquid outlet (9), and liquid outlet (9) is provided with liquid outlet switch (8); Liquid inlet (10) is connected with liquid input media to be measured, and liquid outlet (9) is connected with waste liquid bottle;
Electrode fixed body (11) is embedded in shell (5) above and connects signal processor (6) by wire.
9. biology sensor according to claim 8, is characterized in that, described electrode (2) is made by conductive material.
10. biology sensor according to claim 8, is characterized in that, described contrast electrode (3) is saturated calomel electrode, and the internal-filling liquid body of described saturated calomel electrode is saturated potassium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410445152.2A CN104198554B (en) | 2014-09-03 | 2014-09-03 | A kind of working electrode and preparation method thereof, biosensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410445152.2A CN104198554B (en) | 2014-09-03 | 2014-09-03 | A kind of working electrode and preparation method thereof, biosensor |
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| CN104792840A (en) * | 2015-04-14 | 2015-07-22 | 南京理工大学 | Nanocomposite gamma-Fe2O3/PDA-GA/CuNPs modified electrode, as well as preparation method and application thereof |
| CN106018509A (en) * | 2016-05-20 | 2016-10-12 | 江苏出入境检验检疫局工业产品检测中心 | Urease biosensor based on polyaniline-modified screen-printed electrode and application of urease biosensor |
| CN107493648A (en) * | 2017-01-12 | 2017-12-19 | 中金瑞峰资本管理有限公司 | A kind of sparking electrode for being used to sterilize and preparation method thereof |
| CN109827898A (en) * | 2019-03-29 | 2019-05-31 | 河海大学 | A kind of metal corrosion test device |
| CN110018214A (en) * | 2019-05-20 | 2019-07-16 | 中南大学 | A kind of method of modified coal Quito pore electrod measurement ascorbic acid content |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104792840A (en) * | 2015-04-14 | 2015-07-22 | 南京理工大学 | Nanocomposite gamma-Fe2O3/PDA-GA/CuNPs modified electrode, as well as preparation method and application thereof |
| CN106018509A (en) * | 2016-05-20 | 2016-10-12 | 江苏出入境检验检疫局工业产品检测中心 | Urease biosensor based on polyaniline-modified screen-printed electrode and application of urease biosensor |
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| CN108414587B (en) * | 2016-05-20 | 2019-01-04 | 江苏出入境检验检疫局工业产品检测中心 | A kind of preparation method of urease biologic sensor |
| CN108490042B (en) * | 2016-05-20 | 2019-03-12 | 江苏出入境检验检疫局工业产品检测中心 | A kind of purposes of urease biologic sensor |
| CN107493648A (en) * | 2017-01-12 | 2017-12-19 | 中金瑞峰资本管理有限公司 | A kind of sparking electrode for being used to sterilize and preparation method thereof |
| CN109827898A (en) * | 2019-03-29 | 2019-05-31 | 河海大学 | A kind of metal corrosion test device |
| CN110018214A (en) * | 2019-05-20 | 2019-07-16 | 中南大学 | A kind of method of modified coal Quito pore electrod measurement ascorbic acid content |
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